Supramolecular Functional Materials

ABSTRACT

The field of this invention relates to supramolecular functional materials, particularly to coordination networks, more particularly to coordination polymers, more particularly to metal based one-dimensional coordination polymers. The metal based one-dimensional coordination polymers comprises a repeat unit [L 1 -M-L 2 ] n  where L 1  and L 2  are one of a plurality of carboxylate ligands and L 1  can be the same as L 2 , M is a metal, particularly a transition metal, and n is an integer from 1 to infinity. The metal based one-dimensional coordination polymers display one or more physico-chemical properties giving at least one functionality to the supramolecular material. Furthermore, a method of forming the metal based one-dimensional coordination polymers is provided by a chemical reaction between said organic ligand and said metal where said method comprises at least one selectable chemical reaction condition from the group comprising: volume of reaction vessel, material composition of reaction vessel, temperature, pressure, humidity and gas defining an atmosphere inside reaction vessel.

RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.12/862,251 filed on Aug. 24, 2010, which claims the benefit of U.S.Provisional Application No. 61/275,090, filed on Aug. 24, 2009.

The entire teachings of the above applications are incorporated hereinby reference.

FIELD OF THE INVENTION

This invention relates to supramolecular functional materials,particularly to coordination networks, more particularly to coordinationpolymers, and more particularly to metal based one-dimensionalcoordination polymers.

BACKGROUND OF THE INVENTION

Supramolecular chemistry is a relatively young branch of chemistryhaving undergone much of its development in the latter half of the 20thcentury [1]. The reason for this is twofold, firstly a thoroughunderstanding of synthetic methods resulting in supramolecular systemswas needed and secondly, powerful analytical technology used instructure elucidation and in physico-chemical property determinationneeded to be developed [1]. Analytical techniques that have beensuccessfully employed in this regard include UV-visible, florescence-,and infra-red spectroscopy, nuclear magnetic resonance, powder X-raydiffraction and most importantly single-crystal X-ray diffraction [1].Subsequently, the interest in supramolecular chemistry and theunderstanding of and rational design of property specific materials hasincreased over the last fifty years making supramolecular chemistry oneof the fastest growing and most interdisciplinary areas in chemistry [1,2, 3]. The quest to be able to manipulate and predict the nature ofintermolecular forces in the design of property specific supramolecularentities remains one of the greatest scientific challenges of our day[1, 4, 5, 6].

One of the most studied areas at the moment is the formation of novelmetal-organic frameworks (MOF's) and coordination polymers due to thepossibility of using metal ions to align molecules in a desireddirection [3, 7, 8]. One-dimensional (1D) coordination polymers havebeen extensively researched and subject to many review articles. It hasbeen envisaged that these supramolecular materials could be used asmolecular ferromagnets, metallic and superconducting polymers,non-linear optical materials and ferroelectric materials [9]. In morerecent times the research focus has been aimed at magnetism and inparticular room-temperature and near-room temperature molecular magnets[10-12]. The close packing of metal ions in a one-dimensionalcoordination polymer is favoured for the formation of functionalmaterials characterized by displaying at least one physico-chemicalproperty known to the group comprising: molecular ferromagnets, metallicand superconducting polymers, non-linear optical materials,ferroelectric materials and molecular magnets.

One of the chief problems encountered in this area of research isfinding reliable methods for producing materials with interesting andpossibly useful properties. Additionally, new materials showingpromising physico-chemical properties are often extremely difficult tocharacterize and the exact formula and/or crystal structure of many ofthese materials remains unknown. Methods of ensuring successfulsingle-crystal formation suitable for single-crystal X-ray diffractionneed to be developed.

REFERENCES

-   1. Marais, C. G. (2008). The thermodynamics and kinetics of    sorption. M.Sc thesis. University of Stellenbosch, South Africa.-   2. Lehn, J-M. (1993). Science, 260, 1762.-   3. Kitagawa, S., Kitaura, R., & Noro, S-I. (2004). Angew. Chem. Int.    Ed., 43, 2334.-   4. Ball, P. (1996). Nature, 381, 648.-   5. Maddox, J. (1988). Nature, 335.-   6. Gavezzotii, A. (1994). Acc. Chem. Res., 27,309.-   7. Ferey, G. (2008). Chem. Soc. Rev., 37, 191.-   8. Janiak, C. (2003). Dalton Trans., 2781.-   9. Chen, C-T., Suslick, K. S., (1993). Coord. Chem. Rev., 128, 293.-   10. Jain, R., Kabir, K., Gilroy, J. B., Mitchell, K. A. R., Wong,    K-C., Hicks, R. G. (2007). Nature, 445, 291.-   11. Harvey, M. D., Crawford, T. D., Yee, G. T. (2008). Inorg. Chem.,    47, 5649.-   12. Miller, J. S. (2008) In Engineering of Crystalline Materials    Properties (ed J. J. Novoa, D. Braga and L. Addadi), Springer    Science & Business Media B.V., Dordrecht, The Netherlands, pp.    291-306.

The relevant teachings of the above references are incorporated hereinby reference.

OBJECT OF INVENTION

It is an object of this invention to provide novel supramolecularfunctional materials comprising metal-based one-dimensional coordinationpolymers and at least one reliable method for their formation to atleast alleviate the current disadvantage found in the current state ofthe art.

SUMMARY OF THE INVENTION

In accordance with this invention there is provided at least onesupramolecular functional material comprising at least one,one-dimensional, metal-based coordination network.

There is further provided for the, or each, metal-based coordinationnetwork to be a metal-based one-dimensional coordination polymer,preferably comprising at least one organic ligand and at least one metalion.

There is also provided for the metal-based coordination polymer toinclude at least one solvent molecule.

There is also provided for the metal ion and the organic ligand to forma chain structure when coordinated to one another to form themetal-based one-dimensional coordination polymer.

There is also provided for the metal ion, the organic ligand and thesolvent molecule to form a chain structure and, thus form themetal-based one-dimensional coordination polymer.

There is also provided for the organic ligand to act, in use, as abridging group between the metal ion forming the chain structure, forthe organic ligand to be a carboxylate ligand.

There is also provided for the metal ion to be a transition groupelement, preferably selected from the group consisting of: titanium,vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc andcadmium.

There also provided for the metal-based coordination polymer to exhibit,in use, magnetic, electronic and/or optical physico-chemical properties.

The invention extends to a method of producing at least onesupramolecular functional material comprising at least one metal-basedcoordination network, preferably a one-dimensional metal-basedcoordination network, alternatively a two-dimensional metal-basedcoordination network, further alternatively a three dimensionalmetal-based coordination network.

There is also provided for the method of producing the, or each,metal-based coordination network to be a metal-based one-dimensionalcoordination polymer, preferably comprising at least one organic ligandand at least one metal ion.

There is also provided for the method to include, in use, at least onesolvent molecule.

There is also provided for the method wherein the metal ion and theorganic ligand forms a chain structure when coordinated to one anotherforming the metal-based one-dimensional coordination polymer.

There is also provided for the method wherein the metal ion, the organicligand and the solvent molecule forms a chain structure and, thusforming the metal-based one-dimensional coordination polymer,alternatively a two-dimensional coordination polymer, furtheralternatively a three-dimensional coordination polymer.

There is also provided for the method wherein the organic ligand acts,in use, as a bridging group between the metal ions forming the chainstructure, for the organic ligand to be a carboxylate ligand.

There is also provided for the method wherein the metal ion is atransition group element, preferably selected from the group consistingof: titanium, vanadium, chromium, manganese, iron, cobalt, nickel,copper, zinc and cadmium.

There also provided the method wherein the metal-based coordinationpolymer to exhibit, in use, magnetic, electronic and/or opticalphysico-chemical properties.

There also provided the method wherein at least one reaction conditionis selectable from a group consisting of: volume of reaction vessel,material composition of reaction vessel, temperature, pressure, humidityand gas defining an atmosphere inside reaction vessel.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing will be apparent from the following more particulardescription of example embodiments of the invention, as illustrated inthe accompanying drawings in which like reference characters refer tothe same parts throughout the different views. The drawings are notnecessarily to scale, emphasis instead being placed upon illustratingembodiments of the present invention.

FIG. 1 a-1 d shows diagrams and schemes relating to structure I;

FIG. 1 a shows the ligand-metal-ligand repeat unit forming themetal-based one-dimensional coordination polymer of the chemical formula[Zn(C₁₀H₉O₃)₂]_(n);

FIG. 1 b shows the coordination environment as a sequence of tetrahedraforming the metal-based one-dimensional coordination polymer of thechemical formula [Zn(C₁₀H₉O₃)₂]_(n);

FIG. 1 c a ball and stick representation of the crystal structure of themetal-based one-dimensional coordination polymer of the chemical formula[Zn(C₁₀H₉O₃)₂]_(n) highlighting the coordination bonds between theligand and metal ion;

FIG. 1 d a packing diagram of the crystal structure of[Zn(C₁₀H₉O₃)₂]_(n) as viewed down the crystallographic c-axis;

FIG. 2 a-2 d shows diagrams and schemes relating to structure II;

FIG. 2 a shows the ligand-metal-ligand repeat unit forming themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₁₀H₉O₃)₂]_(n);

FIG. 2 b shows the coordination environment as a sequence of polyhedraforming the metal-based one-dimensional coordination polymer of thechemical formula [Co(C₁₀H₉O₃)₂]_(n);

FIG. 2 c a ball and stick representation of the crystal structure of themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₁₀H₉O₃)₂]_(n) highlighting the coordination bonds between theligand and metal ion;

FIG. 2 d a packing diagram of the crystal structure of[Co(C₁₀H₉O₃)₂]_(n) as viewed down the crystallographic b-axis;

FIG. 3 a-3 d shows diagrams and schemes relating to structure III;

FIG. 3 a shows the ligand-metal-ligand repeat unit forming themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₈H₇O₂)₂]_(n);

FIG. 3 b shows the coordination environment as a sequence of polyhedraforming the metal-based one-dimensional coordination polymer of thechemical formula [Co(C₈H₇O₂)₂]_(n);

FIG. 3 c a ball and stick representation of the crystal structure of themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₈H₇O₂)₂]_(n) highlighting the coordination bonds between the ligandand metal ion;

FIG. 3 d a packing diagram of the crystal structure of [Co(C₈H₇O₂)₂]_(n)as viewed down the crystallographic c-axis;

FIG. 4 a-4 d shows diagrams and schemes relating to structure IV;

FIG. 4 a shows the ligand-metal-ligand repeat unit forming themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n);

FIG. 4 b shows the coordination environment as a sequence of polyhedraforming the metal-based one-dimensional coordination polymer of thechemical formula [Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n);

FIG. 4 c a ball and stick representation of the crystal structure of themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n) highlighting the coordination bonds betweenthe ligand and metal ion;

FIG. 4 d a packing diagram of the crystal structure of[Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n) as viewed down the crystallographic a-axis;

FIG. 5 a-5 d shows diagrams and schemes relating to structure V;

FIG. 5 a shows the ligand-metal-ligand repeat unit forming themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n);

FIG. 5 b shows the coordination environment as a sequence of polyhedraforming the metal-based one-dimensional coordination polymer of thechemical formula [Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n);

FIG. 5 c a ball and stick representation of the crystal structure of themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n) highlighting the coordination bonds betweenthe ligand and metal ion;

FIG. 5 d a packing diagram of the crystal structure of[Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n) as viewed down the crystallographic b-axis;

FIG. 6 shows the coordination environment of structure III partly in aspace-filling representation and partly in a ball and stickrepresentation, and;

FIG. 7 shows the crystallographic data for structures I to V.

DETAILED DESCRIPTION OF THE INVENTION

A description of example embodiments of the invention follows.

The teachings of all patents, published applications and referencescited herein are incorporated by reference in their entirety.

While this invention has been particularly shown and described withreferences to example embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

Referring to the drawings, (1 a) to (1 d) shows structure I of chemicalformula [Zn(C₁₀H₉O₃)2]_(n). FIG. (1 a) shows the ligand-metal-ligandrepeat unit [L₁-M-L₂]_(n) forming a metal-based one-dimensionalcoordination polymer of the chemical formula [Zn(C₁₀H₉O₃)₂]_(n) where nis any integer 1 to infinity, the metal is Zn²⁺ and the ligand (L₁ andL₂) is o-methoxy-cinnamate. Coordination bonds formed between oxygenatoms of the carboxylate group comprising the ligand(o-methoxy-cinnamate) and the metal (zinc) ion are indicated by brokenlines. The coordination environment of the metal-based one-dimensionalcoordination polymer of the chemical formula [Zn(C₁₀H₉O₃)₂]_(n) is shownin (1 b) as a sequence of polyhedra wherein the polyhedra are alltetrahedral. FIG. 1 c) shows a ball and stick representation of thecrystal structure of the metal-based one-dimensional coordinationpolymer of the chemical formula [Zn(C₁₀H₉O₃)₂]_(n) highlighting thecoordination bonds between the ligand and metal ion. The distancebetween zinc ions (Zn—Zn) comprising the metal-based one-dimensionalcoordination polymer was measured as 3.469 Å. FIG. 1 d) shows a packingdiagram of the crystal structure of [Zn(C₁₀H₉O₃)₂] as viewed down thecrystallographic c-axis. This is considered to be a very unusualstructure as the ligands (o-methoxy-cinnamate) are arranged around theZn²⁺ in a propeller like 3₁ screw axis arrangement resulting in a chiralstructure crystallised in the chiral space group P3₁. There is providedthat metal-based one-dimensional coordination polymer of the chemicalformula [Zn(C₁₀H₉O₃)₂]_(n) where n is any integer 1 to infinity, themetal is Zn²⁺ and the ligand is o-methoxy-cinnamate may crystallize inother space groups and comprise polymorphs of the P3₁ structure.Crystallisation of [Zn(C₁₀H₉O₃)₂] was achieved by heating a solutioncontaining zinc metal and o-methoxy-cinnamatic acid at about 80° C. forabout one week.

FIGS. 2 a) to (2 d) shows structure II of chemical formula[Co(C₁₀H₉O₃)₂]_(n). FIG. 2 a shows the ligand-metal-ligand repeat unitforming the metal-based one-dimensional coordination polymer of thechemical formula [Co(C₁₀H₉O₃)₂]_(n) where n is any integer 1 toinfinity, the metal is Co²⁺ and the ligand is o-methoxy-cinnamate.Coordination bonds formed between oxygen atoms of the carboxylate groupcomprising the ligand (o-methoxy-cinnamate) and the metal (cobalt) ionare indicated by broken lines. The coordination environment of themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₁₀H₉O₃)₂]_(n) is shown in (2 b) as a sequence of polyhedral whereinthe polyhedra are an alternating sequence of corner sharing tetrahedraand octahedra. FIG. 2 c) shows a ball and stick representation of thecrystal structure of the metal-based one-dimensional coordinationpolymer of the chemical formula [Co(C₁₀H₉O₃)₂] highlighting thecoordination bonds between the ligand and metal ion.

The distance between cobalt ions (Co—Co) comprising the metal-basedone-dimensional coordination polymer was measured as 3.169 Å and 3.199Å. One of the interesting features of this crystal structure is that thearrangement of molecules around the cobalt ions causes the cobalt ionsto be extremely close to one another along the chain comprising themetal-based one-dimensional coordination polymer. It is this distancewhich facilitates magnetic, electronic and/or optical physico-chemicalproperties or any combination of said physico-chemical propertiescharacteristic of the metal-based one-dimensional coordination polymerof the chemical formula [Co(C₁₀H₉O₃)₂]. FIG. 2 d) shows a packingdiagram of the crystal structure of [Co(C₁₀H₉O₃)₂] as viewed down thecrystallographic b-axis. The crystal structure crystallises in themonoclinic, centrosymmetric space group P2₁/c. There is provided thatmetal-based one-dimensional coordination polymer of the chemical formula[Co(C₁₀H₉O₃)₂] where n is any integer 1 to infinity, the metal is Co²⁺and the ligand is o-methoxy-cinnamate may crystallise in other spacegroups and comprise polymorphs of the P2₁/c structure.

FIGS. 3 a) to (3 d) shows structure III of chemical formula[Co(C₈H₇O₂)₂]_(n). FIG. 3 a) shows the ligand-metal-ligand repeat unitforming the metal-based one-dimensional coordination polymer of thechemical formula [Co(C₈H₇O₂)₂]_(n) where n is any integer 1 to infinity,the metal is Co²⁺ and the ligand is p-toluate. Coordination bonds formedbetween oxygen atoms of the carboxylate group comprising the ligand(p-toluate) and the metal (cobalt) ion are indicated by broken lines.The coordination environment of the metal-based one-dimensionalcoordination polymer of the chemical formula [Co(C₈H₇O₂)₂]_(n) is shownin (3 b) as a sequence of polyhedra wherein the polyhedra are analternating sequence of corner sharing tetrahedra and octahedra. FIG. 3c) shows a ball and stick representation of the crystal structure of themetal-based one-dimensional coordination polymer of the chemical formula[Co(C₈H₇O₂)₂]_(n) highlighting the coordination bonds between the ligandand metal ion. The distance between cobalt ions (Co—Co) comprising themetal-based one-dimensional coordination polymer was measured as 3.143Å. One of the interesting features of this crystal structure is that thearrangement of molecules around the cobalt ions causes the cobalt ionsto be extremely close to one another along the chain comprising themetal-based one-dimensional coordination polymer. It is this distancewhich facilitates magnetic, electronic and/or optical physico-chemicalproperties or any combination of said physico-chemical propertiescharacteristic of the metal-based one-dimensional coordination polymerof the chemical formula [Co(C₈H₇O₂)₂]_(n). FIG. 3 d) shows a packingdiagram of the crystal structure of [Co(C₈H₇O₂)₂]_(n) as viewed down thecrystallographic c-axis. The crystal structure crystallises in theorthorhombic, centrosymmetric space group Pbcn. There is provided thatmetal-based one-dimensional coordination polymer of the chemical formula[Co(C₈H₇O₂)₂]_(n) where n is any integer 1 to infinity, the metal isCo²⁺ and the ligand is p-toluate may crystallise in other space groupsand comprise polymorphs of the Pbcn structure.

FIGS. 4 a) to (4 d) shows structure IV of chemical formula[Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n). FIG. 4 a) shows the ligand-metal-ligandrepeat unit forming the metal-based one-dimensional coordination polymerof the chemical formula [Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n) where n is any integer1 to infinity, the metal is Co²⁺ and the ligand isnaphthalene-1-carboxylic acid. Coordination bonds formed between oxygenatoms of the carboxylate group comprising the ligand(naphthalene-1-carboxylic acid) and the metal (cobalt) ion are indicatedby broken lines. The coordination environment of the metal-basedone-dimensional coordination polymer of the chemical formula[Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n) is shown in (4 b) as a sequence of polyhedrawherein the polyhedra are an alternating sequence of corner sharingtetrahedra and octahedra. FIG. 4 c) shows a ball and stickrepresentation of the crystal structure of the metal-basedone-dimensional coordination polymer of the chemical formula[Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n) highlighting the coordination bonds betweenthe ligand and metal ion and between the isopropanol solvent and themetal ion. The distance between cobalt ions (Co—Co) comprising themetal-based one-dimensional coordination polymer was measured as 3.224Å, 3.470 Å and 3.475 Å. FIG. 4 d) shows a packing diagram of the crystalstructure of [Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n) as viewed down thecrystallographic a-axis. The crystal structure crystallises in theorthorhombic, non-centrosymmetric space group Pna2₁. There is providedthat metal-based one-dimensional coordination polymer of the chemicalformula [Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n) where n is any integer 1 to infinity,the metal is Co²⁺ and the ligand is naphthalene-1-carboxylic acid maycrystallise in other space groups and comprise polymorphs of thestructure Pna2₁.

FIGS. 5 a) to (5 d) shows structure V of chemical formula[Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n). FIG. 5 a) shows the ligand-metal-ligandrepeat unit forming the metal-based one-dimensional coordination polymerof the chemical formula [Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n) where n is anyinteger 1 to infinity, the metal is Co²⁺ and the ligand isanthracene-2-carboxylic acid. Coordination bonds formed between oxygenatoms of the carboxylate group comprising the ligand(anthracene-2-carboxylic acid) and the metal (cobalt) ion are indicatedby broken lines. The coordination environment of the metal-basedone-dimensional coordination polymer of the chemical formula[Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n) is shown in (5 b) as a sequence of polyhedrawherein the polyhedra are an alternating sequence of edge sharingtetrahedra and octahedra. FIG. (5 c) shows a ball and stickrepresentation of the crystal structure of the metal-basedone-dimensional coordination polymer of the chemical formula[Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n) highlighting the coordination bonds betweenthe ligand and metal ion and between the isopropanol solvent and themetal ion. The distance between cobalt ions (Co—Co) comprising themetal-based one-dimensional coordination polymer was measured as 3.482 Åand 5.169 Å. FIG. 5 d) shows a packing diagram of the crystal structureof [Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n) as viewed down the crystallographicb-axis. The crystal structure crystallises in the monoclinic,non-centrosymmetric space group P2₁. There is provided that metal-basedone-dimensional coordination polymer of the chemical formula[Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n) . where n is any integer 1 to infinity, themetal is Co²⁺ and the ligand is anthracene-2-carboxylic acid maycrystallize in other space groups and comprise polymorphs of thestructure P2₁.

FIG. 6 shows the coordination environment of structure III partly in aspace-filling representation and partly in a ball and stickrepresentation to indicate that the Co²⁺ ions at closer than the sum oftheir van der Waals radii facilitating magnetic, electronic and/oroptical physico-chemical properties or any combination of saidphysico-chemical properties characteristic of the metal-basedone-dimensional coordination polymer herein described.

FIG. 7 shows the crystallographic data for structures I to V.

EXAMPLES

Embodiments of the invention will be illustrated by the followingnon-limiting examples of their synthesis and crystallisation. Severalmetal-based one-dimensional coordination polymers comprising zinc andcobalt metal ions and various aromatic carboxylates as ligands, havebeen crystallised via selective chemical reactive/interactiveconditions.

The at least one supramolecular material comprising metal-basedcoordination networks in the form of metal-based one-dimensionalcoordination polymers are generally made via the direct reaction of theligands (L) with the metal (M). The usual method of crystallisation isvia reaction of a ligand (L) with a metal salt (M⁺).

A typical non-limiting example of the crystallisation method used toform the supramolecular material of structure V is given.

0.2 g of anthracene-9-carboxylic acid and 0.027 g of Co metal(previously washed using 2M hydrochloric acid) were inserted into aTeflon hydrothermal bomb reactor. To this was added 10 ml ofisopropanol. The reactor was then partially immersed in an oil bath andheated at 130° C. for 48 hours, followed by slow cooling to roomtemperature over 2 hours. The reaction product was then collected byfiltration resulting in fine purple needle-like crystals (0.058 g). Asingle crystal of this was then selected and a single-crystal X-raydiffraction data set collected and solved. This structure, structure V,is presented in FIGS. 5 a) to (5 d).

Manganese supramolecular functional materials, as well as the zincsupramolecular functional materials described herein, were obtained bysynthetic methods similar to those described in the preceding paragraph.

Not all structures employed the use of the Teflon hydrothermal bomb. Forexample structure I was crystallised by heating a solution containingzinc metal and o-methoxy-cinnamic acid at 80° C. for a week.

What is claimed is:
 1. A method of producing at least one supramolecularfunctional material comprising at least one polymeric repeat unit, theat least one polymeric repeat unit comprising at least one ligand and atleast one metal ion, wherein said method comprises a chemical reactionbetween an at least one ligand and an at least one metal.
 2. The methodof producing at least one supramolecular functional material accordingto claim 1, wherein the at least one ligand is a carboxylate ligand andthe at least one metal is a transition metal.
 3. The method of producingat least one supramolecular functional material according to claim 1,wherein the chemical reaction takes place in the presence of at leastone solvent.
 4. The method of producing at least one supramolecularfunctional material according to claim 3, wherein the method comprisesat least one selectable chemical reaction condition.
 5. The method ofproducing at least one supramolecular functional material according toclaim 4, wherein the at least one selectable chemical reaction conditionis selected from the group comprising: volume of a reaction vessel,material composition of a reaction vessel, temperature, pressure,humidity and gas defining an atmosphere inside a reaction vessel.
 6. Asupramolecular functional material of the chemical formula[Zn(C₁₀H₉O₃)₂]_(n) crystallised in the space group P3₁ wherein n is anyinteger from 1 to infinity.
 7. A supramolecular functional material ofthe chemical formula [Co(C₁₀H₉O₃)₂]_(n) crystallised in the space groupP2₁/c wherein n is any integer from 1 to infinity.
 8. A supramolecularfunctional material of the chemical formula [Co(C₁₁H₇O₂)₂(C₃H₇O)]_(n)crystallised in the space group Pna2₁ wherein n is any integer from 1 toinfinity.
 9. A supramolecular functional material of the chemicalformula [Co(C₁₅H₉O₂)₄(C₃H₇O)₂]_(n) crystallised in the space group P2₁wherein n is any integer from 1 to infinity.
 10. The method of producingat least one supramolecular functional material according to claim 3,wherein the reaction takes place in the presence of a carboxylic acid.11. The method of producing at least one supramolecular functionalmaterial according to claim 10, wherein the chemical reaction takesplace inside a hydrothermal bomb reactor.
 12. The method of producing atleast one supramolecular functional material according to claim 10,wherein the chemical reaction comprises crystallisation from a heatedsolution containing the at least one ligand and the at least one metal.